Resin and pipes for transporting water containing chlorine dioxide

ABSTRACT

This invention is related to the preparation of polyethylene pipe resins suitable for transporting hot and cold water containing chlorine dioxide.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Continuation of U.S. application Ser. No.12/677,192, filed on Jun. 3, 2010, now issued as U.S. Pat. No.8,459,283, which claims the benefit of PCT/EP2008/061537, filed on Sep.2, 2008, which claims priority from EP 07116894.2, filed on Sep. 21,2007, and EP 07121860.6 filed on Nov. 29, 2007.

This invention is related to the preparation of polyethylene pipe resinssuitable for transporting cold and/or hot water containing chlorinedioxide.

Polymer materials are frequently used for preparing pipes that aresuitable for transporting fluid such as liquid or gas. The fluid may bepressurised and its temperature may range between 0 and 90° C. Thesepipes were usually prepared from medium or high density monomodal ormultimodal polyethylene.

For example, WO00/01765 discloses the use of a multimodal polyethyleneresin having a density of 0.930 to 0.965 g/cc and a MI5 of from 0.2 to1.2 dg/min for transporting cold, pressurised water.

The transport of hot water requires other types of resin thanconventional polyethylene as the service life of a typical polyethylenepipe decreases by about 50% when the temperature of the transportedfluid increases by 10° C. and as it is subject to stress cracking atelevated temperature.

Several polyethylene resins were disclosed for the transport of hotfluid. For example, EP-A-1448702 discloses a polyethylene resin usefulfor the preparation of hot water pipes. That polyethylene resin ismultimodal with a high molecular weight fraction having a density of atleast 0.920 g/cc and a low molecular weight fraction. Its density rangesbetween 0.921 and 0.950 g/cc. Its time to failure at a temperature of95° C. and at a pressure of 3.6 MPa is of at least 165 h and its modulusof elasticity is of at most 900 MPa.

EP-A-1425344 also discloses a multimodal polyethylene resin that can beused for hot water pipes. It has a density of from 0.925 to 0.950 g/ccand a MI2 of from 0.1 to 5 dg/min. It comprises a high molecular weightfraction having a density of from 0.910 to 0.935 g/cc and a MI2 of atmost 1 dg/min and a low molecular weight fraction having a density offrom 0.945 to 0.965 g/cc and a MI2 of from 2 to 200 dg/min.

Water for domestic use also transports disinfectants such as for examplechlorine dioxide. The service life of pipes prepared from the prior artpolyethylene resins was substantially decreased by the addition ofchlorine dioxide.

Cross-linked polyethylene resins have also been used to improve theperformances of the pipes. The cross linking was achieved eitherchemically with silane or peroxides or physically by irradiation.

WO2005/056657 discloses the use of a high density polyethylene resincomprising a combination of at least two antioxidant additives toprepare pipes for transporting water containing chlorine.

There is thus a need for polyethylene pipes that are able to transporthot or cold water containing such aggressive chemical compound, that donot require the addition of specific combinations of antioxidants.

It is an aim of the present invention to prepare polyethylene piperesins suitable for transporting hot or cold water containing chlorinedioxide.

It is also an aim of the present invention to prepare polyethlene piperesins that have good mechanical properties.

It is another aim of the present invention, to prepare polyethylene piperesins that can be processed easily.

Any one of these aims is at least partially fulfilled by the presentinvention.

Accordingly, the present invention discloses the use for transportingwater containing chlorine dioxide of a pipe characterised in that isprepared from a polyethylene resin produced by one or more single sitecatalyst systems.

The pipe of the present invention is preferably prepared from a bi- ormulti-modal polyethylene resin produced either by two or more singlesite catalyst systems in a single reactor or by a single site catalystsystem in two serially connected reactors, wherein at least one of thesingle site catalyst systems is a metallocene catalyst system comprisinga bisindenyl or a bis tetrahydroindenyl catalyst component of formulaR″(Ind)₂MQ₂ wherein Ind is a substituted or unsubstituted indenyl ortetrahydroindenyl group, R″ is a structural bridge impartingstereorigidity to the complex, M is a metal Group 4 of the PeriodicTable and Q is a hydrocarbyl having from 1 to 20 carbon atom or ahalogen.

The one or more single site catalyst systems are preferably metallocenecatalyst systems and more preferably comprise a bridged bis-indenyl orbistetrahydro-indenyl catalyst component described by general formulaR″(Ind)₂MQ₂wherein Ind is a substituted or unsubstituted indenyl ortetrahydroindenyl group, R″ is a structural bridge impartingstereorigidity to the complex, M is a metal Group 4 of the PeriodicTable and Q is a hydrocarbyl having from 1 to 20 carbon atom or ahalogen.

If Ind is an indenyl group it is preferably unsubstituted or substitutedat position 4 with a bulky substituent and at position 2 with a smallsubstituent. A bulky substituent is at least as bulky as t-butyl. Asmall substituent is preferably methyl.

If Ind is a tetrahydroindenyl group, it is preferably unsubstituted.

M is preferably Ti or Zr, more preferably Zr.

Each Q is preferably selected from aryl, alkyl, alkenyl, alkylaryl orarylalkyl having at most 6 carbon atoms, or halogen. More preferablyboth Q are the same and are chlorine.

Structural bridge R″ is selected from C₁-C₄ alkylene radical, a dialkylgermanium or silicon or siloxane, or an alkyl phosphine or amineradical, which bridge is substituted or unsubstituted. Preferably it isethylene, isopropylidene, dimethylsilyl or diphenyl.

The most preferred catalyst component is ethylene bistetrahydroindenylzirconium dichloride. The metallocene catalyst component used in thepresent invention can be prepared by any known method. A preferredpreparation method is described in J. Organomet. Chem. 288, 63-67(1985).

The catalyst system also comprises an activating agent having anionising action and optionally an inert support. The activating agent ispreferably selected from aluminoxane or boron-containing compound andthe inert support is preferably selected from mineral oxide, morepreferably, silica. Alternatively, the activating agent is a fluorinatedactivating support.

The polyethylene resin that can be used in the present invention iseither monomodal or bi- or multi-modal and is prepared by any methodknown in the art, with the restriction that the catalyst systemcomprises at least one single site component. Its density preferablyranges from 0.915 to 0.965 g/cc.

In a more preferred embodiment according to the present invention thepolyethylene resin is a bi- or multi-modal resin prepared in two or moreserially connected loop reactors. It comprises a high molecular weight(HMW), low density fraction and a low molecular weight (LMW), highdensity fraction.

The high molecular weight, low density fraction has a density of atleast 0.908 g/cc, preferably of at least 0.912 g/cc and of at most 0.928g/cc, more preferably of at most 0.926 g/cc. Most preferably it is ofabout 0.922 g/cc. It has a high load melt index HLMI of at least 2dg/min, more preferably of at least 5 dg/min and most preferably of atleast 7 dg/min and of at most 12 dg/min, more preferably of at most 10dg/min. Most preferably, it is of 8 to 9 dg/min. The melt index MI2 isof from 0.05 to 2 dg/min, more preferably of from 0.1 to 0.5 dg/min andmost preferably of about 0.2 dg/min.

The low molecular weight, high density fraction has a density of atleast 0.930 g/cc, more preferably of at least 0.940 g/cc, and of at most0.975 g/cm³, more preferably of at most 0.962 g/cc. Most preferably itis of about 0.945 to 0.955 g/cc. It has a melt index MI2 of at least 0.5dg/min, more preferably of at least 1 dg/min, and of at most 10 dg/min,more preferably of at most 6 dg/min. Most preferably, it is of from 2 to3 dg/min.

The final resin comprises 50 to 60 wt % of HMW fraction, preferably from50 to 55 wt %, more preferably from 52 to 53 wt % and from 40 to 50 wt %of LMW fraction, preferably from 45 to 50 wt % and most preferably from47 to 48 wt %. It has a broad or multimodal molecular weightdistribution of from 2 to 5, a density of from 0.930 to 0.949 g/cc and amelt index MI2 of from 0.3 to 1 dg/min. The most preferred polyethyleneresin according to the present invention has a density of about 0.935g/cc, a melt index MI2 of 0.6 dg/min and a polydispersity of about 3.

The molecular weight distribution is fully described by thepolydispersity index D defined by the ratio Mw/Mn of the weight averagemolecular weight Mw to the number average molecular weight Mn asdetermined by gel permeation chromatography (GPC).

The density is measured according to the method of standard test ASTM1505 at a temperature of 23° C. The melt index and high load meltindices are measured by the method of standard test ASTM D 1238respectively under a load of 2.16 kg and 21.6 kg and at a temperature of190° C.

The polyethylene resins according to the invention can be prepared byany method suitable therefore. They can be prepared by physicallyblending the high density and the low density polyethylene fractions,prepared separately, or they can be prepared by polymerising ethylene inthe presence of a mixture of catalysts. Preferably, the high density andlow density fractions are produced in two serially connected loopreactors with the same catalyst system. In such a case, the LMW, highdensity fraction is preferably prepared in the first reactor, so thatthe HMW, low density fraction is prepared in the presence of the highdensity fraction. Preferably, the same catalyst system is used in bothsteps of the cascade polymerisation process to produce a chemical blendof the high and low molecular weight fractions. The catalyst system maybe employed in a solution polymerisation process, which is homogeneous,or in a slurry process, which is heterogeneous or in a gas phaseprocess. Preferably a slurry process is used. The most preferredpolymerisation process is carried out in two serially connected slurryloop reactors.

In a preferred arrangement, the product of a first cascade reactionzone, including the olefin monomer, is contacted with the secondco-reactant and the catalyst system in a second cascade reaction zone toproduce and mix the second polyolefin with the first polyolefin in thesecond reaction zone. The first and second reaction zones areconveniently interconnected reactors such as interconnected loopreactors. It is also possible to introduce into the second reaction zonefresh olefin monomer as well as the product of the first reaction zone.

Because the second polyolefin is produced in the presence of the firstpolyolefin a multimodal or at least bimodal molecular weightdistribution is obtained.

In one embodiment of the invention, the first co-reactant is hydrogen,to produce the LMW fraction and the second co-reactant is the comonomerto produce the HMW fraction. Typical comonomers include hexene, butene,octene or methylpentene, preferably hexene.

In an alternative embodiment, the first co-reactant is the comonomer,preferably hexene. Because the metallocene catalyst components of thepresent invention exhibit good comonomer response as well as goodhydrogen response, substantially all of the comonomer is consumed in thefirst reaction zone in this embodiment. Homopolymerisation takes placein the second reaction zone with little or no interference from thecomonomer.

The temperature of each reactor may be in the range of from 60° C. to110° C., preferably from 70° C. to 90° C.

The present invention further provides the use of such a polyethyleneresin for the manufacture of pipes for transporting cold or hot water,especially containing chlorine dioxide.

The polyethylene resins according to the invention, having such aspecific composition, molecular weight and density, can lead to a markedimprovement of the processing properties when the resin is used as apipe resin, while conserving or improving mechanical behaviour ascompared to known pipe resins.

In particular, the polyethylene resins in accordance with the inventionhave impact resistance and slow crack resistance at least equivalent,often higher than current available pipe resins.

The resins of the invention are endowed with excellent rheologicalbehaviour.

The resin in accordance with the invention is characterised by a highshear-thinning behaviour. This means good injection-moulding capabilityfor the resins when used to produce injection-moulded pipes and pipefittings.

Generally, the pipes are manufactured by extrusion or by injectionmoulding, preferably by extrusion in an extruder. The pipes made of themultimodal polyethylene resin according to the present invention may besingle layer pipes or be part of multilayer pipes that include furtherlayers of other resins.

In another embodiment according to the present invention, the pipe is amultilayer pipe comprising at least one layer of polyethylene pipe resinprepared by any method known in the art and at least one other layer ofpolyethylene resin prepared with a single site catalyst system, whereinsaid other polyethylene resin may or may not be a pipe resin.

The pipe resin may also be compounded, for example with black or bluepigments.

The pipes of the present invention offer an excellent resistance tocorrosion When used for transporting hot or cold water containingchlorine dioxide. The water temperature ranges from 0 to 90° C. and theamount of chlorine dioxide in the water is of from the smallestdetectable amount, typically of from 0.1 mg/L, up to the existing uppertolerance of 1 mg per litre of water, typically it is of 0.3 to 0.4mg/L. It must be noted that the pipes according to the present inventioncould sustain higher percentage of chlorine dioxide than the upper limitof 1 mg/L tolerated for domestic water.

EXAMPLES

Three different resins have been extruded into pipes that were testedfor transporting water containing chlorine dioxide.

Resin R1, according to the present invention, was prepared with ethylenebistetrahydroindenyl zirconium dichloride catalyst component in a doubleslurry loop reactor. The density was of 0.935 g/cc and the melt flowrate MI2 was of 0.7 dg/min. It was additivated with black pigments andthe final density was 0.945 g/cc.

Resin R2 is a commercial resin sold by Total Petrochemicals under thename XS10B. It was prepared with a Ziegler-Natta catalyst system.

Resin R3 is a commercial resin sold by Total Petrochemicals under thename 3802B. It was prepared with a chromium-based catalyst system.

Resins R2 and R3 were also additivated with the same amount of blackpigments as resin R1.

These pipes were tested following the standard procedure of JANALAB andunder the following conditions:

-   -   pH: 6.8    -   chlorine dioxide: 4 ppm    -   fluid temperature: 70° C.    -   stress: 1.9 MPa    -   flow rate: 0.1 USGPM

The results of time to failure are summarised in Table I

TABLE I Resin Average time to failure (h) R1 955 R2 884 R3 842

As can be seen from Table I the resin according to the present inventionresists for a longer time than those prepared with Ziegler-Natta orchromium catalyst systems.

The invention claimed is:
 1. A bi- or multi-modal polyethylene resincomprising: a high molecular weight (HMW), low density fraction, whereinthe HMW, low density fraction has a density of from 0.908 to 0.928 g/ccand a high load melt index HLMI of from 2 to 12 dg/min; and a lowmolecular weight (LMW), high density fraction, wherein the LMW, highdensity fraction has a density of from 0.930 to 0.975 g/cc and a meltindex MI₂ of from 0.5 to 10 dg/min; wherein the bi- or multi-modalpolyethylene resin has a density of from 0.930 to 0.949 g/cc and a meltindex MI₂ of from 0.3 to 1 dg/min; wherein the HMW, low density fractionand the LMW, high density fraction are produced either with two or moresingle site catalyst systems in a single reactor or with a single sitecatalyst system in two serially connected reactors; and wherein at leastone of the single site catalyst systems is a metallocene catalystsystem.
 2. The bi- or multi-modal polyethylene resin of claim 1, whereinthe metallocene catalyst system comprises a bisindenyl or a bistetrahydroindenyl catalyst component of formula R″(Ind)₂MQ₂; and whereinInd is a substituted or unsubstituted indenyl or tetrahydroindenylgroup, R″ is a structural bridge imparting stereorigidity to thecomplex, M is a metal of Group 4 of the Periodic Table and Q is ahydrocarbyl having from 1 to 20 carbon atom or a halogen.
 3. The bi- ormulti-modal polyethylene resin of claim 1, wherein the bi- ormulti-modal polyethylene resin comprises from 50 to 60 wt. % of the HMW,low density fraction and 40 to 50 wt. % of the LMW, high densityfraction.
 4. The bi- or multi-modal polyethylene resin of claim 1,wherein the bi- or multi-modal polyethylene resin is prepared in two ormore serially connected slurry loop reactors.
 5. The bi- or multi-modalpolyethylene resin of claim 1, wherein the LMW, high density fraction isprepared in a first reactor and the HMW, low density fraction isprepared in the presence of the LMW, high density fraction.
 6. The bi-or multi-modal polyethylene resin of claim 5, wherein the HMW, lowdensity fraction and the LMW, high density fraction are produced in twoserially connected loop reactors with the same catalyst system.
 7. Thebi- or multi-modal polyethylene resin of claim 1, wherein the two ormore single site catalyst systems are each metallocene catalyst systems,or wherein the single site catalyst system is a metallocene catalystsystem.
 8. A pipe comprising the bi- or multi-modal polyethylene resinof claim
 1. 9. The pipe of claim 8, wherein the pipe is a single layerpipe.
 10. The pipe of claim 8, wherein the pipe is a multi layer pipe,and wherein at least one of the layers is prepared with the bi- ormulti-modal polyethylene resin.
 11. The pipe of claim 8, wherein thepipe is prepared by extrusion or injection molding the bi- ormulti-modal polyethylene resin.
 12. A method of preparing a bi- ormulti-modal polyethylene resin comprising blending: a high molecularweight (HMW), low density fraction of the bi- or multi-modalpolyethylene resin, wherein the HMW, low density fraction has a densityof from 0.908 to 0.928 g/cc and a high load melt index HLMI of from 2 to12 dg/min; and a low molecular weight (LMW), high density fraction ofthe bi- or multi-modal polyethylene resin, wherein the LMW, high densityfraction has a density of from 0.930 to 0.975 g/cc and a melt index MI₂of from 0.5 to 10 dg/min; wherein the bi- or multi-modal polyethyleneresin has a density of from 0.930 to 0.949 g/cc and a melt index MI₂ offrom 0.3 to 1 dg/min; wherein the HMW, low density fraction and the LMW,high density fraction are produced either with two or more single sitecatalyst systems in a single reactor or with a single site catalystsystem in two serially connected reactors; and wherein at least one ofthe single site catalyst systems is a metallocene catalyst system. 13.The method of claim 12, wherein the blending comprises physicalblending.
 14. The method of claim 12, wherein the blending compriseschemical blending in a solution polymerisation process, slurrypolymerisation process or a gas phase process.
 15. The method of claim12, wherein the bi- or multi-modal polyethylene resin is prepared in twoor more serially connected slurry loop reactors.
 16. The method of claim12, wherein the LMW, high density fraction is prepared in a firstreactor and the HMW, low density fraction is prepared in the presence ofthe LMW, high density fraction.
 17. The method of claim 16, wherein theHMW, low density fraction and the LMW, high density fraction areproduced in two serially connected loop reactors with the same catalystsystem.
 18. A method of preparing a pipe comprising extruding orinjection molding a bi- or multi-modal polyethylene resin, wherein thebi- or multi-modal polyethylene resin comprises: a high molecular weight(HMW), low density fraction, wherein the HMW, low density fraction has adensity of from 0.908 to 0.928 g/cc and a high load melt index HLMI offrom 2 to 12 dg/min; and a low molecular weight (LMW), high densityfraction, wherein the LMW, high density fraction has a density of from0.930 to 0.975 g/cc and a melt index MI₂ of from 0.5 to 10 dg/min;wherein the bi- or multi-modal polyethylene resin has a density of from0.930 to 0.949 g/cc and a melt index MI₂ of from 0.3 to 1 dg/min;wherein the HMW, low density fraction and the LMW, high density fractionare produced either with two or more single site catalyst systems in asingle reactor or with a single site catalyst system in two seriallyconnected reactors; and wherein at least one of the single site catalystsystems is a metallocene catalyst system.